Treatment of materials made of or containing cellulose derivatives



Patented Oct. 18, 1932 PATENT OFFICE HENRY DBEYFUS, OF LONDON, ENGLANDTREATMENT OF MATERIALS OF OR CONTAINING CELLULOSE DmIVATIVES No Drawing.Application flled'iiarch 12, 1927, Serial No. 175,014, and in GreatBritain. December 14, 1988.

This invention relates to the dyeing, printing or stencilling ofthreads, yarns, knitted or woven fabrics or other products made of orcontaining cellulose acetate or other organic acid esters of cellulose,such for example as cellulose formate, propionate or butyrate or theproduct obtained by the treatment oi alkalised cellulose with p-toluenesulphochloride (e. g. the product known as immunised cotton or made ofor containing cellulose ethers, such as methyl, ethyl, or benzyl cellu--lose, or the corresponding condensation products of cellulose andglycols or other polyhydric alcohols, all of which cellulose derivativesare hereinafter referred to as organic substitution derivatives ofcellulose.

According to the present invention materials made of or containing oneor more of the said organic substitution derivatives of cellulose aredyed or otherwise colored with coloring matters or compounds containingone or more omega-amino groups, that is to say compounds in which anaryl dye nucleus or component thereof is connected through a side chainto a basic amino group or a basic aliphatically substituted amino group.The linking chain may be a carbon atom or atoms alone or may contain inaddition to carbon other atoms such as nitrogen or oxygen.

Further according to the invention such coloring matters may be producedonthe fibre or material by combination of components one or more ofwhich contain such w-amino groups.

Such coloring matters or compounds may be produced by any convenientmethod. Thus for example they may be prepared by reduc tion of nitriles(e. g. by treatment of the nitrile in alcoholic solution with zinc andhydrochloric acid or with sodium). w-Aminoalkylamino compounds may insome cases be produced by treatment of an amino compoui'id containing ornot containing an ortho 5 carboxylic group or of a phenolic compoundwith an alkylene diamine in presence of a sulphite. w-Aminoalkyl ethercompounds or w-aminoalkylamino compounds may be produced by treatment ofa phenolic or aniino to compound with an amino alkyl halide.

Emple 1. 1 Methylamino-4-chloranthraquinone is heated for some hours atabout 140 C. with cuprous cyanide in presence of pyridin. Ammonia isadded to the reaction product. The nitrile obtained is then reduced withzinc and hydrochloric acid to obtain the dyestufl o )IH-CH:

Ha-NH:

which can be used to dye cellulose acetate in red shades in thefollowing manner:

75 grams of finely divided dyestufi are stirred with one kilogram ofsodium sulphoricinoleate (50%). The mixture is heated until ashomogeneous as possible and slowly diluted with boiling water to 10litres. The whole is now added through. a filter cloth to 125 litres ofwater and 5 kilograms of cellulose acetate yarn in hank form areentered. The temperature is raised during of an hour to 7580 C. andafter dyeingat, this temperature for of an hour, the hanks are rinsedwell, washed off in soft water and dried.

Ewample 2. 1.4 Aminohydroxyanthraquinone is boiled with chloracetylchloride for hour using xylene as diluent. The product is reduced to theleuco body and the latter heated under pressure with an alcoholicsolution of methylamine. The product is oxidized to obtain the dyestuflIO NH-CO-OHz-NH-CH:

NH-CH:

- a-naphthylamine.

100 grams of the finely powdered dyestuff I are added to a dispersion of5 cc. Xylene in 400 cc. sodium sulphoricinoleate (50%). The Whole isheated to 90 O. with stirring and stirred until as homogeneous aspossible.

with epichloramine to obtain the dyestufi N H CHr CHOH-OHIOH isobtained.

B. A20 dyestuffs Example 3.Potassium p-nitrophenolate is condensed with,B-brom-ethylamine, the product reduced, diazotised and coupled withDyeings obtained with this dyestufi NHz- 011mm- 0ON=N may be diazotisedon the fibre and developed with any suitable developer, for examplemaminoethylaniline.

Ewample 4.0-Amin0-a-phenylethylamine is diazotised and coupled withmaminoethylaniline in the form of its acetate to yield the dyestufiNHa-CHCH:

ON=NONHCHrOElrNHz 0. Miscellaneous dyestuffs Example 5.-Anthrapyrimidoneis condensed with epichloramine (CH Cl-CHOH-CH NH to produce the dye I NOHz-CHOECBr-NH:

Example 6.4.4- Diamino-2'- nitrodiphenylmethane is condensed with excessof ,8- bromethylamine. The dyestufi obtained (H N-CHa-CHOH-CHz-NH:

v which gives yellow shades.

. solution when they are sufliciently soluble or in the form of saltssuch as the hydrochlorides or acetates, or in aqueous suspension or theymay be brought into colloidal solution by any\ of the methods known inthe art such as by grinding (for example in colloid mills), bydissolving in av solvent and pouring into water containing or notcontaining protective colloids, by pretreating with so1ubilising agents,or by other methods. Of the solubilising agents which are suitable forobtaining such dispersions I may mention those described in U. S.Patents 1,618,414 and 1,694,413 and British Patents Nos. 273,819 and273,820 both filed April 10, 1926; viz. bodies of oily or fattycharacteristics, namely higher fatty acids orsulphonated or otherderivatives thereof containing salt-forming groups, such assulphoricinoleic or other sulphonated fatty acids or salts of such acidsor. bodies, for instance their alkali or ammonium salts, used alone orin conjunction with auxiliary solvents as described in U. S. Patent No.1,690,481 and application S. No. 152,517 carbocyclic compoundscontaining in their structure one or more saltforming groups or salts ofsuch compounds; sulpho-aromatic fatty acids or salts thereof; andsoluble resin soaps or sodium or other soluble salts or soaps of resinacids.

may be used for producing fast yellow shades on cellulose acetateartificial silk in the following manner:

Though in the above description dyestufi's belonging to particularseries have been given and further aliphatic side chains which, in

Nos. 1,618,413,

addition to the m-amino group or groups, contain only hydrocarbonradicles or ether or alcohol or other amino groups have been described,it is to be understood that the invention extends to the use ofdyestufi's of any series and to dyestuffs or components containingaliphatic side chains which, in addition to the w-fiIIllIlO group orgroups,

, may contain any other desired substituents.

The invention further comprises the dyeing or otherwise coloring ofmixed goods comprising for example, in addition to one or more organicsubstitution derivatives of cellulose, silk, wool or cellulose fibresnatural or artificial such as cotton or the cellulose type of artificialsilk, in solid or contrasting shades according to the aflinity of thenonester and non-ether portion of the goods. The goods may be dyed withother dyestufl's for the non-ester and non-ether portion thereof eitherbefore, after or together with the dyestuffs of the present invention.

The term dyeing in the claims is to be understood to include printingand stencilling and also to include the case when the actual dyecompound is produced on the material itself by interaction ofcomponents, as for example when dyeing by the azoic process.

What I claim and desire to secure by Letters Patent is 1. Process fordyeing material comprising an organic substitution derivative ofcellulose, comprising dyeing the material with,

a coloring compound which comprises at least one basic amino grouplinked directly to carbon in a side chain.

2. Process according to claim 1, characterised in that the coloringcompound is applied in aqueous solution.

3. Process according to claim 1, characterised in that the coloringcompound is applied in aqueous colloidal solution.

4. Process for dyeing material comprising an organicsubstitutionderivative of cellulose, comprising dyeing the material withan anthraquinone coloring compound which comprises at least one basicamino group linked directly to carbon in a side chain.

5. Process according to claim 4, characterised in that the coloringcompound is applied in aqueous solution.

6. Process according to claim 4, characterised in that the coloringcompound is applied in aqueous colloidal solution.

7. Process for dyeing material comprising cellulose acetate, comprisingdyeing the material with a coloring compound which comprises at leastone basic amino group linked directly to carbon in a side chain.

8. Process according to claim 7, characterised in that the coloringcompound is applied in a ueous solution.

9. rocess according to claim 7, characterised in that the coloringcompound is applied in aqueous colloidal solution.

10. Process for dyeing material comprising cellulose acetate, comprisingdyeing the material with an anthraquinone coloring compound whichcomprises at least one basic amino group linked directly to carbon in aside chain.

11. Process according to claim 10, characterised in that the coloringcompound is applied in aqueous'solution.

12. Process according to claim 10, characterised in that the coloringcompound is applied in aqueous colloidal solution.

13. Material comprising an organic substi-. tution derivative ofcellulose, dyed with a coloring compound which comprises at least onebasic amino group linked directly to carbon in a side chain.

14; Material comprising cellulose acetate, dyed with a coloring compoundwhich comprises at least one basic amino group linked directly to carbonin a side chain.

In testimony whereof I have hereunto subscribed my name.

HENRY DREYFUS.

Cal

